Dyeing composition and process for keratinaceous material



United States Patent DYEING COMPOSITION AND PROCESS FOR KERATINACEOUSMATERIAL Carl G. Westerberg, Sierra Madre, Calif.

No Drawing. Application July 11, 1951,

Serial No. 236,275

19 Claims. (Cl. 16788) The present invention relates to a novel dyeingcomposition for keratinaceous material, such as hair, wool, fur,feathers and the like. The dye compositions of the present invention arecapable of producing a variety of colors and a variety of shades in thevarious colors, depending upon variations in time, concentration and pHof the dye composition employed. The dyed materials are permanently dyedthe desired color and are particularly desirable for hair dyeing,inasmuch as they are harmless when used as herein described.

It is therefore an object of the present invention to provide novel hairdyeing compositions capable of producing a variety of colors and avariety of shades in the various colors.

It is another object of the present invention to provide a novelhair-dyeing composition which is completely harmless, and which iscapable of simple and easy use by the inexperienced user to produceevenly dyed hair which permanently retains the desired color.

The compositions of the present invention are composed of a plurality ofcomponents. The essential components are three, (1) a water solublethiol compound, such as a water soluble thiol salt or an ester, (2) asoluble heavy metal salt and (3) an alkali. In addition, thecompositions may contain a plurality of additional optional ingredients.A desirable ingredient is a wetting agent of the non-soapy type. Typicalof these wetting agents are alkylaryl sulphonates, sulphated laurylalcohol and sulphonated oils. The composition may be thickened with awater soluble gum as an additional optional ingredient. The particularforms of the compositions will be described in more detail hereinafter.

Considerable variation is possible in each of the essential ingredients.Thus, with reference to the thiol compound, it has been found thatthioglycolic acid employed in the form of its salts such as sodium andammonium salts, is particularly desirable and readily available for thispurpose. However, other thiol compounds which are water soluble may beused. These include the glycerol ester of thioglycolic acid, as Well asother esters of thioglycolic acid. Similarly, 2 -mercaptyl. ethanol(SHCI-IzCHzOH) may be used. In place of these specific materials anyWater soluble compound having a thiol group may be employed.

As to the heavy metal salts that may be employed, these include aconsiderable number, of which cobalt, nickel, iron, manganese andbismuth are particularly desirable. A variety of colors may be obtainedfrom these metals, varying from a bright yellow with bismuth to a verydark brown, almost black color when using nickel. Cobalt and manganesegive a variety of brown colors, Whereas iron produces a reddish browncolor. The heavy metal may be employed in any of a variety of watersoluble salts. Of these the sulphates, chlorides, acetates, lactates,nitrates, some carbonates and subcarbonates may be employed. It will beappreciated that the salt which is selected for any particular metalshould be a water soluble salt.

Fee

Almost any water soluble alkaline material may be employed. Preferablythis alkali is an organic alkali and preferably volatile; such asammonia, amines and the like. Suitable amines include methyl, ethyl,propyl, isopropyl amines or diamines, monoethanolamine, morpholine andnumerous other similar compounds. Inorganic alkaline materials, such assodium and potassium hydroxides, carbonates, phopshates and the like,which do not interfere with the heavy metal salts may be employed.

The dyeing compositions in condition for actual use are in aqueoussolution. Under these circumstances a complex is formed of the alkali,the thiol compound and the metal salt. These complexes are colored andare water soluble. They have an apparent afiinity for any materialcontaining keratin and can be used for dyeing keratinaceous materials bythe simple application of the aqueous solution thereto. For the purposeof obtaining a uniform dyeing, it is preferred to have the compositioncontain a non-soapy wetting agent, which serves to bring the aqueoussolution into uniform contact with all of the filaments. The complexappears to form a further complex with the thiol groups contained in thekeratinaceous material.

For the purpose of marketing these dyeing compositions they may bepackaged in a variety of ways. Some of the finished dyeing compositionsare unstable when kept for extended periods of time, and accordingly itis preferred that they be mixed shortly prior to the time of use. Thusiron and manganese tend to oxidize the thiol group in the thiol compoundand accordingly cause the mixture to lose its dyeing power when storedover extended periods of time. Accordingly, with such compositions it ispreferred to maintain the iron and manganese salts separate from thethiol compounds until immediately prior to use. Antioxidants such aspropylgallate may be used to delay the oxidation of such mixed dyeingcompositions.

In contrast to the instability of these iron and man ganesecompositions, solutions containing soluble nickel salts have been keptfor several months in admixture with the thiol compound without anyapparent deterioration of the dyeing power of the material. It is oftendesirable to package these compositions in the form of two aqueoussolutions, one containing the soluble metal salt and the othercontaining the alkali and the thiol compound. One of these solutions canthen also contain the wetting agent and a water soluble gum as athickening agent. As an alternative the respective solutions may beformulated in the form of a cream with an emulsified oil base or mixedwith a sulphonated oil. In addition the materials may be supplied in theform of the dry ingredients which can be mixed by the user. Any of thisvariety of ways of preparing the composition may be employed.

The dyeing operation may also be effected by first treating the materialto be dyed with the thiol compound and then treating the material,either with or without prior rinsing with the heavy metal salt solution.In this manner, the color develops first right in the material beingdyed rather than as a color complex which is added as such to thematerial. It should be pointed out that where the thiol compound and themetal salt are used separately as described immediately above, the thiolsolution alone need be alkaline for reaction with the keratinaceousmaterial. The heavy metal salt solution may be acid, neutral or alkalineas desired, and the dyeing action is still obtainable.

The pH of the dyeing composition may be varied widely to producedifferent effects. Some of the metals employed in the present dyingcompositions will transmit the dye to white wool yarn under a Wide rangeof pH, ranging from slightly acid to strongly alkaline. A pref- 3 erablepH is from 8 to 10.5. The depth of the color varies directly with thepH, the deepest color being achieved at the highest pH. For example, byvarying the pH of nickel-containing dyeing compositions, it is possibleto vary the color from light brown to a very dark brown or almost black.

Variations in color may also be obtained by varying the amounts of themetal present and the concentration of the complex used. It is preferredto employ the alkali, the thiol compound and the metal compound insubstantially equivalent amounts. It will be apparent that an excess ofany of the components of the composition will not adversely affect theaction of the combination but will be essentially a waste of thatparticular component. Colors may also be varied by the use ofcombinations of metals rather than a single metal. As illustrated in thefollowing examples the metal compound should preferably be present in anamount at least about 3.3 per cent by weight of the total dyeingsolution and preferably from about to per cent. While it is preferred toemploy the alkali, the thiol compound and the metal compound insubstantially equivalent amounts they may be varied considerably asshown in the examples.

In employing the composition it is merely necessary to apply thecomposition to the material to be dyed and usually from 5 to 10 minutesis sufficient time to effect a satisfactory dyeing operation. Usuallybeyond this time period no further dyeing action is obtained. Variationin the color may be obtained by shortening the dyeing period below the 5to 10 minutes which effects the full action of the dye.

The following examples will serve to illustrate the invention:

Example 1 Thioglycolic acid 70% cc 7.0 NHiOH 28% cc 30.0 Sulphonated oilcc 1.0 NiCl2.6H2O gr 10.0

H2O to make 100.0 cc.

Example 2 Thioglycolic acid 70% cc 7.0 NHQOH 28% cc 20.0 Sulphonated oilcc 1.0 NiCl2.6H2O "grams" 10.0

H2O to make 100.0 cc.

White wool yarn was dyed for periods of 5, 10 and minutes. Again thedyeing reaction was substantially complete in the first five minutes andthere was little variation in color between the samples. These sampleswere approximately the same color as the dyed wool samples of Example 1.

Example 3 Thioglycolic acid 70% cc 7.0 NH4OH 28% 10.0 Sulphonated il cc1.0 NiCl2.6H2O grams 10.0

H2O to make 100.0 cc.

White wool yarn was dyed with this solution for periods of 5, 10 and 15minutes. In this instance the dyeing reaction did not appear to becomplete within five minutes but had been approximately completed in tenminutes. All of these samples were somewhat lighter than the samplesdyed in Examples 1 and 2.

4 Example 4 The dyeing solution in Example 3 Was diluted with an equalvolume of water. White wool yarn was dyed with this diluted solution forperiods of 5, l0 and 15 minutes. The sample treated for five minutes wasa light cream to tan color, the ten minute sample was a tan color, andthe fifteen minute sample was a fairly dark tan color.

Example 5 The solution of Example 3 was diluted with twice its volume ofwater and white wool yarn was again dyed for periods of 5, 10 and 15minutes. The solution was effective to tint the yarn, the depth of thetint increasing with the length of time. The fifteen minute sample wasslightly lighter in color than the ten minute sample of Example 4.

Example 6 Glyceryl thioglycolate 50% (Evans Chemetics Thiovanol) cc 10.0NHQOH 28% cc 10.0 NiCl2.6H2O grams 10.0 Sulphonated oil cc 1.0

H20 to make 100.0 cc.

White wool yarn was dyed with this solution for periods of 5, 10 and 15minutes. The five-minute sample was a distinct tan color, whereas the 10and 15 minutes samples were progressively darker.

Example 7 Glyceryl thioglycolate 50% cc 10.0 NH4OH 28% cc 30.0NiCl2.6H2O grams 10.0 Sulphonated oil cc 1.0

H20 to make 100.0 cc.

Example 8 Mercaptoethanol cc 6.0 NH4OH 28% cc 20.0 Sulphonated oil cc1.0 NiCl2.6H2O rams" 10.0

H2O to make 100.0 cc.

White wool yarn was dyed for five minutes with this solution and took ona very dark brown color.

Cotton yarn and wool yarn were treated simultaneously with the dyeingsolution. The wool yarn immediately picked up the dye color, whereas thecotton remained its original white color.

Example 9 Solution A:

Thioglycolic acid 70% cc 7.0 NH4OH 28% cc 20.0 Sulphonated oil cc 1.0H20 to make 100.0 cc.

Solution B:

NiCl2.6H2O grams 10.0 Sulphonated oil cc 1.0

H20 to make 100.0 cc.

Solution A was a water white solution and was applied to hair and wasrinsed out completely. The hair, while still damp was then treated withsolution B which was only slightly colored, and the hair immediatelytook on a deep brown color.

Mix A and B prior to use.

These solutions were made up and were then mixed immediately prior touse. The results obtained with this are the same as those obtained withExample 2. This example demonstrates the possibility of preparingseparate solutions which may be sold as such and which may be mixedimmediately prior to use.

Example 11 Grams Thioglycolic acid 6.0 Cobalt a tat 10.0

Morpholine and water suflicient to make 100.0 cc. and

a pH of 9.5.

White wool yarn dyed with this solution took on a deep brown color.

Example 12 Grams Glyceryl thioglycolate 50% (Evans Chemetics Thiovanol)12.0 Bismuth nitrat 10.0 Isopropylamine and water sufficient to make100.0 cc.

and a pH of 10.

White wool yarn was dyed with this solution and took on a brilliantyellow color.

Example 13 Grams Glyceryl thioglycolate 12.0 Ferric sulphat 10.0

Ammonia and water sufiicient to make 100.0 cc. and

a pH of 10.5.

White wool yarn was dyed with this solution and the yarn immediatelytook on a reddish brown typically iron color.

Example 14 Grams Mercaptoethanol 6.0 Manganous chloride 10.0

Water and ammonia sufiicient to make 100.0 cc. and a pH of 8.

White wool yarn was dyed with this solution and took on a very darkbrown color.

The above examples are also useful for the dyeing of human hair. Forexample, one of the nickel dyeing solutions was employed to dye blondhair. At a pH of 8.5 the hair took on a light brown color, at a pH of9.5 the hair took on a quite deep brown color, whereas at a pH of 10.5the hair became almost black.

In addition, various samples of white wool yarn were dyed with mixturesof bismuth and nickel. By this means it was able to control the depth ofthe brown color so that any minute variation between the bright yellowcolor obtained with the bismuth and the deep brown obtained with nickelwas obtainable.

As many apparently Widely different embodiments of this invention may bemade Without departing from the spirit and scope thereof, it is to beunderstood that I do not limit myself to the specific embodimentsherein.

What I claim is:

1. A dyeing composition for keratinaceous material comprising an aqueoussolution of a water soluble thiol 6 compound, a water soluble salt of ametal selected from the group consisting of cobalt, nickel, iron,manganese and bismuth in an amount equal to at least about 3.3 per centby weight of the total composition and a water soluble alkalinematerial, the solution having a pH Within the approximate range of8-105.

2. A dyeing composition for keratinaceous material comprising an aqueoussolution of a water soluble salt of thioglycolic acid, a water solublesalt of a metal selected from the group consisting of cobalt, nickel,iron, manganese and bismuth in an amount equal to at least about 3.3 percent by weight of the total composition and a volatile alkali, thesolution having a pH Within the approximate range of 8-105.

3. A dyeing composition for keratinaceous material comprising an aqueoussolution of sodium thioglycolate, a water soluble salt of a metalselected from the group consisting of cobalt, nickel, iron, manganeseand bismuth in an amount equal to at least about 3.3 per cent by Weightof the total composition and ammonia, the solution having a pH withinthe approximate range of 8-105.

4. A dyeing composition for keratinaceous material comprising an aqueoussolution of sodium thioglycolate, a water soluble cobalt salt in anamountequal to at least about 3.3 per cent by weight of the totalcomposition and ammonia, the solution having a pH within the approximaterange of 8-105.

5. A dyeing composition for keratinaceous material comprising an aqueoussolution of sodium thioglycolate, a water soluble nickel salt in anamount equal to at least about 3.3 per cent by weight of the totalcomposition and ammonia, the solution having a pH within the approximaterange of 8-105.

6. A dyeing composition for keratinaceous material comprising an aqueoussolution of sodium thioglycolate, a water soluble iron salt in an amountequal to at least about 3.3 per cent by weight of the total compositionand ammonia, the solution having a pH within the approximate range of8-105.

7. A dyeing composition for keratinaceous material comprising an aqueoussolution of sodium thioglycolate, a water soluble manganese salt in anamount equal to at least about 3.3 per cent by weight of the totalcomposition and ammonia, the solution having a pH Within the approximaterange of 8-105.

8. A dyeing composition for keratinaceous material comprising an aqueoussolution of sodium thioglycolate, a water soluble bismuth salt in anamount equal to at least about 3.3 per cent by weight of the totalcomposition and ammonia, the solution having a pH within the approximaterange of 8-105.

9. A dyeing composition for keratinaceous material comprising an aqueoussolution of a water soluble ester of thioglycolic acid, a Water salt ofa metal selected from the group consisting of cobalt, nickel, iron,manganese and bismuth in an amount equal to at least about 3.3 per centby weight of the total composition, and a volatile alkali, the solutionhaving a pH within the approximate range of 8-105.

10. A dyeing composition for keratinaceous material comprising anaqueous solution of glyceryl thioglycolate, a water soluble salt of ametal selected from the group consisting of cobalt, nickel, iron,manganese and bismuth in an amount equal to at least about 3.3 per centby weight of the total composition and ammonia, the solution having a pHwithin the approximate range of 8-105.

11. A dyeing composition for keratinaceous material comprising anaqueous solution of 2-mercaptoethanol, a water soluble salt of a metalselected from the group consisting of cobalt, nickel, iron, manganeseand bismuth in an amount equal to at least about 3.3 per cent by weightof the total composition and ammonia, the solution having a pH withinthe approximate range of 8-105.

12. A process of dyeing keratinaceous material which comprises applyingthereto an aqueous solution of a water soluble thiol compound, a watersoluble salt of a heavy metal in an amount equal to at least about 3.3per cent by weight of the total composition and a water soluble alkalinematerial, the solution having a pH within the approximate range of8-10.5.

13. The process of dyeing keratinaceous material which comprisesapplying thereto an aqueous solution of a soluble salt .of thioglycolicacid, a soluble salt of a metal selected from the group consisting ofcobalt, nickel, iron, manganese and bismuth in an amount equal to atleast about 3.3 per cent by weight of the total composition, and a watersoluble alkaline material, the solution having a pH within theapproximate range of 810.5.

14. The process of dyeing keratinaceous material which comprisesapplying thereto an aqueous solution of a soluble salt of thioglycolicacid, a soluble salt of a metal selected from the group consisting ofcobalt, nickel, iron, manganese and bismuth in an amount equal to atleast about 3.3 per cent by Weight of the total composition, and avolatile alkali, the solution having a pH within the approximate rangeof 8-10.5.

15. The process of dyeing keratinaceous material which comprisesapplying thereto an aqueous solution of a soluble salt of thioglycolicacid, a soluble salt of a metal selected from the group consisting ofcobalt, nickel, iron, manganese and bismuth in an amount equal to atleast about 3.3 per cent by weight of the total composition, and andammonia, the solution having a pH within the approximate range of8-10.5.

16. The process of dyeing keratinaceous material which comprisesapplying thereto an aqueous solution of ammonium thioglycolate, a watersoluble salt of a metal selected from the group consisting of cobalt,nickel, iron, manganese and bismuth in an amount equal to at least about3.3 per cent by weight of the total composition and ammonia, theSolution having a pH within the approximate range of 810.5.

17. The process of dyeing keratinaceous material which comprisesapplying thereto an aqueous solution of sodium thioglycolate, a watersoluble salt of a metal selected from 8 the group consisting of cobalt,nickel, iron, manganese and bismuth in an amount equal to at least about3.3 per cent by weight of the total composition and ammonia, thesolution having a pH within the approximate range of 53-105.

18. The process of dyeing keratinaceous material which comprisesapplying thereto an aqueous solution of glyceryl thioglycolate, a watersoluble salt of a metal selected from the group consisting of cobalt,nickel, iron, manganese and bismuth in an amount equal to at least about3.3 per cent by weight of the total composition and ammonia, thesolution having a pH within the approximate range of 8-10.5.

19. The process of dyeing keratinaceous material which comprisesapplying thereto an aqueous solution of 2- mercaptoethanol, a watersoluble salt of a metal selected from the group consisting of cobalt,nickel, iron, manganese and bismuth in an amount equal to at least about3.3 per cent by weight of the total composition and ammonia, thesolution having a pH within the approximate range of 810.5.

References Cited in the fileof this patent UNITED STATES PATENTS1,937,365 Stoddard Nov. 28, 1933 2,261,094 Speakman Oct. 28, 19412,540,980 Den Beste Feb. 6, 1951 FOREIGN PATENTS 117,071 Australia June3, 1943 318,045 France Oct. 4, 1902 OTHER REFERENCES Hall: TextileColorist, February 1942, pp. 63-65.

Winter: Hair Dyes of Today, Soap Perfumery and Cosmetics, December 1938,pp. 1080-1084 and 1088; pp. 1081, 1082 and 1084 particularly pertinent.

Allen: Review of Hair Dyes, Soap Perfumery and Cosmetics, September1938, pp. 815-817, and 819; p. 819 particularly pertinent.

1. A DYEING COMPOSITION FOR KERATINACEOUS MATERIAL COMPRISING AN AQUEOUSSOLUTION OF A WATER SOLUBLE THIOL COMPOUND, A WATER SOLUBLE SALT OF AMETAL SELECTED FROM THE GROUP CONSISTING OF COBALT, NICKEL, IRON,MANGANESE AND BISMUTH IN AN AMOUNT EQUAL TO AT LEAST ABOUT 3.3 PER CENTBY WEIGHT OF THE TOTAL COMPOSITION AND A WATER SOLUBLE ALKALINEMATERIAL, THE SOLUTION HAVING A PH WITHIN THE APPROXIMATE RANGE OF8-10.5.